EP0129448A1 - Process for selectively extracting copper using 4-acyl(3H)-pyrazol-3-ones - Google Patents

Abstract

Liquid / liquid extraction process for copper from an aqueous sulfuric etching solution of the ore or concentrated semi-product to be treated. The extraction is carried out in an organic solvent, containing in solution an extraction agent derived from 2-phenyl-4-acyl (3H) pyrazol-3-ones, the phenyl being able to be substituted or not. Application to the valuation of minerals.

Description

The present invention relates to the selective extraction of copper.

The invention relates more particularly to the selective extraction of copper from ores or semi-products concentrated in it, by a liquid / liquid extraction technique.

During the last twenty years, significant research has been done for the recovery of increasingly poor ores (at around 1% copper), difficult to concentrate or too complex to be treated by conventional pyrometallurgy processes.

The development of extraction agents (hereinafter called extractors) from copper and with a high load capacity has made it possible to develop solvent extraction processes.

Several families of organic extractants have been proposed to achieve a concentration of leaching solutions by liquid / liquid extraction. For the best known, these are hydroxylated oxime-type chelating agents, among which are particularly recommended those placed on the market by General Mills under the general name of the LIX series, and those marketed respectively by Shell under the name SME 529 and by ICI under the name _A CORGA P 5000, or hydroxyquinoline type chelating agents, such as for example those sold by _A shland Chemical under the names KELEX 100 and KELEX 120.

Currently, 15% of world copper production, or 1.2 M _T , is obtained by hydrometallurgy with the help of these extracting agents. Extraction on an industrial scale is then mainly carried out from sulfuric media for dissolving the ore by means of extractants dissolved in organic diluents such as aliphatic or aromatic hydrocarbons with a high flammability point such as kerosene, naphtha and the like. Among the most used commercial products, we can cite SOLVESSO 150 and ESCAID 100 from ESSO.

• 1°) pour des extractants de la série des LIX, notamment le LIX 64 N qui est le plus développé des produits de cette série :
  • . une faible capacité de charge en cuivre, en dépit d'une très bonne sélectivité vis-à-vis de Ni et Co, ce qui oblige à opérer avec des volumes de phase organique et aqueuse dans un rapport élevé ou avec une concentration exagérément élevée en extractant ; dans un cas comme dans l'autre, il en découle qu'il faut investir plus qu'il n'est normal soit pour l'installation d'extraction, soit pour l'extractant à mettre en oeuvre, avec pourtant, au bout du compte, un résultat encore insuffisant.
  • . une légère extraction concomitante du fer qui nécessite de retraiter la solution aqueuse de réextraction avant la phase d'électrolyse qui est la phase classique de purification du métal extrait,
  • . la nécessité d'opérer à une température inférieure à 40°C, le LIX 63 présent à raison de 1 % dans le LIX 64 N étant instable au-delà de cette température,
• 2°) pour les autres extractants de structure voisine que sont le produit commercialement dénommé SME 529 et ceux de la série des ACORGA (voir plus haut),
  • . bien qu'ils donnent des coefficients d'extraction plus élevés que les produits de la série des LIX et qu'ils présentent des cinétiques d'extraction et de réextraction plus intéressantes que ceux-ci, on a toutefois à déplorer une réextraction très difficile, d'où il s'ensuit un taux résiduel de cuivre en phase aqueuse trop élevé (voir J.A. Tumilty, Advance in extractive metallurgy, 1977, p.123).
  • . on a ainsi été conduit à ajouter des proportions assez importantes d'un agent modifiant (en pratique du 4-nonylphénol), mais l'amélioration de la réextraction qui est susceptible d'en résulter a pour contrepartie une baisse du coefficient d'extraction,
• 3°) pour les extractants du type KELEX, et notamment le KELEX 100, utilisés pour les minerais sulfurés qui donnent des solutions plus concentrées en cuivre (de l'ordre de 30 à 50 g/1), on rajoute du 4-nonylphénol pour éviter la formation d'une troisième phase.

The drawbacks of the extractants used today are essentially:

• 1) for extractants from the LIX series, in particular the LIX 64 N which is the most developed of the products in this series:
  • . a low copper loading capacity, in spite of a very good selectivity with respect to Ni and Co, which requires operating with volumes of organic and aqueous phase in a high ratio or with an excessively high concentration of extracting; in one case as in the other, it follows that it is necessary to invest more than is normal either for the extraction installation, or for the extractant to be implemented, with however, at the end of the account, still an insufficient result.
  • . a slight concomitant extraction of the iron which requires reprocessing the aqueous re-extraction solution before the electrolysis phase which is the conventional phase of purification of the extracted metal,
  • . the need to operate at a temperature below 40 ° C, the LIX 63 present at a rate of 1% in the LIX 64 N being unstable above this temperature,
• 2) for the other extractants with a similar structure, that is the product commercially known as SME 529 and those of the ACORGA series (see above),
  • . although they give higher extraction coefficients than the products of the LIX series and they present more interesting extraction and re-extraction kinetics than these, we nevertheless have to deplore a very difficult re-extraction, from which there follows a too high residual rate of copper in the aqueous phase (see JA Tumilty, Advance in extractive metallurgy, 1977, p.123).
  • . we have thus been led to add fairly large proportions of a modifying agent (in practice 4-nonylphenol), but the improvement in the re-extraction which is likely to result has as a counterpart a reduction in the extraction coefficient,
• 3) for KELEX type extractants, and in particular KELEX 100, used for sulphide ores which give more concentrated solutions of copper (of the order of 30 to 50 g / l), 4-nonylphenol is added for avoid the formation of a third phase.

• . soit à améliorer les performances de l'extractant principal du point de vue de la capacité de charge, de la sélectivité et de la cinétique d'extraction,
• . soit à empêcher la formation d'un précipité à l'interface ou d'une troisième phase.

The work carried out over the past few years for the sulfuric extraction of non-ferrous metals, and mainly copper, has thus focused, for the most part, on tests to improve existing systems and aimed to remedy as much as harm to the known faults of these systems, and this by testing additives to such systems aimed

• . either to improve the performance of the main extractant from the point of view of carrying capacity, selectivity and extraction kinetics,
• . either to prevent the formation of a precipitate at the interface or of a third phase.

On the other hand, there has been described in patent DD-A-142,059 a process for recovering metals, and more particularly lead, zinc and copper without selectivity, by leaching of complex ores by means of a solution of agents. extraction agents chosen from complexing agents of the polydentate type dissolved in organic solvents, such as dialkyldithiophosphoric acids, 4-acyl pyrazolones or dithiocarbamates, in solution in chlorinated hydrocarbons, aliphatic or aromatic hydrocarbons, alcohols or ketones .

In this process, the minerals are not treated beforehand with alkaline or acid solutions.

It is not a liquid / liquid extraction, but an attack on the ore crushed by an organic solution of a complexing agent and then, after separation of the solid residue, extraction of the metals from said organic solution using a solution of a dilute mineral acid (2N). This process leads to non-selective extraction and requires the use of an additional reprocessing step so that each of the metals extracted can be obtained pure.

The aim of the present invention is the selective extraction, and with a high yield, of copper from ores or semi _- products concentrated in containing it, by a liquid / liquid extraction technique.

The problem thus posed is resolved by a liquid / liquid extraction process comprising a prior attack on the ore or the concentrated semi-product by an acid leaching agent in an aqueous medium, preferably sulfuric acid, and according to which the copper from the etching solution by liquid / liquid extraction using at least one suitable 2-phenyl 4-acyl 5-alkyl or phenyl (3H) -pyrazol-3-one, in organic solution, the phenyl groups being able to be substituted or not by alkyl groups.

The process according to the invention has been found to unexpectedly provide an extraction selectivity with respect to iron and a copper extraction efficiency which are quite exceptional, an extraction capacity better than that of conventional techniques, a greater ease and lower cost of implementation having regard to the possibility of avoiding or at least limiting below what was essential hitherto the addition of compounds with modifying action such as nonylphenol.

It has been found according to the invention that these results, as well as others which the rest of the present text may reveal, are achieved by a process which constitutes the first object of the present invention and according to which a liquid / liquid extraction is carried out copper from an aqueous sulfuric etching solution of the ore or concentrated semi-product to be treated, using at least one extraction agent of type 2-phenyl 4-acyl 5-alkyl or phenyl (3H) - pyrazol-3-one in an organic solvent capable of diluting and dissolving this extraction agent and, as much as possible, the complex that it forms with the copper to be extracted.

More specifically, the extractant useful in accordance with the invention corresponds to the formula:

• - où R₁ représente un groupe phényle, éventuellement substitué par un ou plusieurs groupes alkyles contenant chacun 1 à 12 atomes de carbone
• - où R₂ représente un groupe alkyle ramifié ou non contenant 1 à 12 atomes de carbone, un groupe phényle éventuellement substitué par un ou plusieurs groupes alkyles contenant chacun 1 à 12 atomes de carbone
• - où Z représente un groupe alkylène linéaire ou ramifié, saturé ou insaturé contenant 1 à 21 atomes de carbone
• - et où R₃ représente H, un (2-phényl 5-alkyl (3H)-pyrazolyl-3-one) carbonyl-4, ou un (2-phênyl 5-phényl (3H)-pyrazolyl-3-one) carbonyl-4 formant ainsi un bis acyl pyrazolone de formule :
  

this β-dicarbonyl compound can just as easily exist in one of the two keto-enolic forms:

• - where R ₁ represents a phenyl group, optionally substituted by one or more alkyl groups each containing 1 to 12 carbon atoms
• - where R ₂ represents a branched or unbranched alkyl group containing 1 to 12 carbon atoms, a phenyl group optionally substituted by one or more alkyl groups each containing 1 to 12 carbon atoms
• - where Z represents a linear or branched, saturated or unsaturated alkylene group containing 1 to 21 carbon atoms
• - And where R ₃ represents H, a (2-phenyl 5-alkyl (3H) -pyrazolyl-3-one) carbonyl-4, or a (2-phenyl 5-phenyl (3H) -pyrazolyl-3-one) carbonyl -4 thus forming a bis acyl pyrazolone of formula:
  

the phenyls which may or may not be substituted by alkyl groups.

According to an advantageous embodiment of the invention, R ₁ represents the phenyl group and R ₂ an alkyl group of 1 to 5 carbon atoms, preferably the methyl group; according to another advantageous form of the invention, R ₁ represents a phenyl group substituted by an alkyl group of 8 to 12 carbon atoms.

Finally, Z preferably represents an alkylene group of 6 to 17 carbon atoms and more particularly ethyl-1-pentylene undecylene or heptadecylene, with R ₃ = H, and a group - (CH ₂ ) ₄ when R ₃ represents a pyrazolyl carbonyl group as defined above.

For clarity, it should be noted that we have chosen to currently designate these products as being derivatives of 4-acyl (3H) -pyrazol-3-ones, and this in near conformity with the official nomenclature in force since 1972, when the nomenclature used before this date assigned to the products of this type the name of 4-acyl-2-pyrazolin-5-ones. These are obviously the same products.

Some of these compounds are new.

• - 2-phényl 4-(2-éthylhexanoyl) 5-méthyl (3H)-pyrazol-3-one
• - 2-phényl 4-(isononanoyl) 5-méthyl (3H)-pyrazol-3-one
• - di 1,6-(2-phényl 5-mêthyl 4-pyrazolyl-3-one) hexane 1,6-dione
• - 2-phényl 4(undécénoyl)5-méthyl (3H)-pyrazole-3-one
• - 2-phényl 4-(oléoyl)5-phényl (3H)-pyrazol-3-one
• - di-1,10-(2-phényl 5-phényl 4-pyrazolyl-3-one) décane 1,10 dione.

The invention therefore also relates to the new products falling within the scope of the above formula, and more particularly the following:

• - 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) -pyrazol-3-one
• - 2-phenyl 4- (isononanoyl) 5-methyl (3H) -pyrazol-3-one
• - di 1,6- (2-phenyl 5-methyl 4-pyrazolyl-3-one) hexane 1,6-dione
• - 2-phenyl 4 (undecenoyl) 5-methyl (3H) -pyrazole-3-one
• - 2-phenyl 4- (oleoyl) 5-phenyl (3H) -pyrazol-3-one
• - di-1,10- (2-phenyl 5-phenyl 4-pyrazolyl-3-one) decane 1.10 dione.

These compounds can be prepared from products known by techniques known to those skilled in the art, for example, by the method described by Jensen in Acta Chemica Scandinavica, 13, 1668 (1959) in which the chloride of acid of formula HZ-COCl, in the case of monopyrazolones, or C10CZCOC1, in the case of dipyrazolones, on the heterocycle unsubstituted in position 4 and in the presence of calcium hydroxide.

According to the invention, an organic solvent is used to dilute and dissolve the extractant and the complex that the latter forms with copper; it must be practically insoluble in water and not disturb the action of the extractant. This organic solvent should preferably have a high flash point.

Generally, the organic solvent should be able to dissolve from about 20 g / l to about 750 g / l and preferably from about 50 g / l to about 200 g / l of the extractant.

Effective organic solvents are aliphatic or aromatic hydrocarbons with a high flash point, such as kerosene, naphtha and the like.

Among these solvents, the products commercially available under the name SOLVESSO and distributed by the company ESSO are particularly recommended, and more particularly the one which corresponds to the trade name SOLVESSO 150 and which is an aromatic petroleum solvent.

The extraction process according to the invention takes place by bringing the organic solvent containing the extractant into contact with the aqueous solution of leaching agent containing copper, preferably a sulfuric solution and the other metallic species and resulting from the attack of the ore. The two phases, the aqueous phase and the organic phase, can be brought into contact by solvent extraction techniques well known to those skilled in the art (continuous or discontinuous extraction, use of mixer-settlers or columns of 'extraction, etc ...; the circulation of fluids is preferably against the current).

The ratio of the volumes of the aqueous and organic phases depends on the apparatus used, on the concentration of extracting agent in the organic phase and on the composition of the aqueous phase to be treated. A Vaq / Vorg report. between approximately 3/1 and 1/3 is desirable.

The temperature at which the phases are brought into contact and the separation thereof is not a primary factor; it is simply related to the flash point of the solvent used; a temperature between 20 and 60 ° C is suitable in practice.

It appeared that, for some of the acylpyrazolones recommended according to the invention, there may be a precipitation of the complex formed between the copper and the extracting agent, after a certain period of time. It has been found, and this constitutes a variant of the process according to the invention, that this precipitation can then be delayed without inhibiting the action of the extractant by adding to the solution of this extractant in the organic solvent a proportion of 2 to 20% by volume and preferably 10% by volume, of 4-nonylphenol or an equivalent.

• - les solutions d'acide sulfurique issues de minerais oxydés, à faible concentration en cuivre (1 à 10 g/1) contenant du fer, du cobalt et du nickel à des teneurs variables et dont le pH est compris entre 1 et 3 ;
• - les solutions d'acide sulfurique issues de minerais sulfurés, à forte concentration en cuivre (15 à 40 g/1) contenant aussi de fortes proportions de fer, nickel et cobalt et dont le pH est compris entre 1 et 3.

The aqueous phase subjected to the process according to the invention can be of two types; in fact, depending on the nature of the ores or concentrates of ores to be treated, and in particular the copper ores to be treated, there are two types of sulfuric solutions for the extraction of copper by hydrometallurgical means:

• - sulfuric acid solutions from oxidized ores, with a low copper concentration (1 to 10 g / 1) containing iron, cobalt and nickel at variable contents and whose pH is between 1 and 3;
• - sulfuric acid solutions from sulphide ores, with a high copper concentration (15 to 40 g / 1) also containing high proportions of iron, nickel and cobalt and whose pH is between 1 and 3.

At higher pHs, the solutions would be less stable; at lower pHs, the extraction coefficient would be lower.

The invention is illustrated more concretely below, with reference to preferred embodiments and to nonlimiting examples of implementation.

pour des solutions aqueuses sulfuriques à faible teneur en cuivre (environ 3 g/1) ;

• - le KELEX 100
  
  pour des solutions aqueuses sulfuriques à forte teneur en cuivre, provenant de minerais cuprifères sulfurés.

The extraction properties of the means recommended according to the invention have been compared with those of products currently used industrially for the same purposes, namely: LIX 64N (which comprises 1% of LIX 63)

for aqueous sulfuric solutions with a low copper content (approximately 3 g / 1);

• - the KELEX 100
  
  for aqueous sulfuric solutions with a high copper content, coming from sulfurized copper ores.

The corresponding comparative extraction tests were carried out on synthetic solutions representative of the industrial compositions to be treated usually and formulated as follows:

According to a preliminary study on possible diluents meeting the definition given above, we were led to prefer the aromatic petroleum solvent sold under the name SOLVESSO 150.

As a variant, finding its usefulness essentially in cases where it is advisable to combat the formation (generally occurring after several hours, for example after 12 to 24 hours) of a more or less significant precipitate in the organic phase, we have found advantageous to also add to the organic extraction medium from about 2 to about 20%, and preferably about 10%, by volume of nonylphenol.

• -.Figure 1 représente l'influence de la concentration en agent d'extraction 2-phényl 4-lauroyl 5-méthyl (311) pyrazol-3-one dans du SO_LVESSO 150 portée en abscisse, ainsi que celle du pH de la phase aqueuse à traiter (phase aqueuse de type A) sur l'extraction (% du Cu extrait porté en ordonnée)
• - Figure 2 représente les isothermes d'extraction obtenues par traitement d'une solution aqueuse sulfurique de type A à pH 2,5, respectivement :
  • 1°) Pour la courbe en trait pointillé, avec du produit commercial LI_X 64 _N à 15 % dans du diluant commercialisé sous la dénomination ESCAID 100 ;
  • 2°) Pour la courbe en trait continu, avec de la 2-phényl 4-lauroyl 5-méthyl(3H)pyrazol-3-one à 50 g/1 dans du SOLVESSO 150 + 10 ml/100 ml volume de nonylphénol ;
• - Figures 3 et 4 représentent les isothermes de réextraction obtenus lors de mise en contact successives d'une même phase aqueuse sulfurique avec une nouvelle phase organique chargée en cuivre.

The other tests carried out are described below with reference to the figures in the accompanying drawing plates, in which:

• Figure 1 represents the influence of the concentration of 2-phenyl 4-lauroyl 5-methyl (311) pyrazol-3-one extractant in SO _LVE SSO 150 plotted on the abscissa, as well as that of the pH of the aqueous phase to be treated (type A aqueous phase) on the extraction (% of Cu extracted on the ordinate)
• - Figure 2 represents the extraction isotherms obtained by treatment of an aqueous sulfuric solution of type A at pH 2.5, respectively:
  • 1 °) For the curve in dotted lines, with 15% LI _X 64 _N commercial product in diluent marketed under the name ESCAID 100;
  • 2 °) For the curve in solid line, with 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one at 50 g / 1 in SOLVESSO 150 + 10 ml / 100 ml volume of nonylphenol;
• - Figures 3 and 4 show the re-extraction isotherms obtained during successive contacting of the same sulfuric aqueous phase with a new organic phase loaded with copper.

In the case of FIG. 3, the aqueous phase is not initially loaded with copper.

In the case of FIG. 4, the copper charge of the aqueous phase is initially 30 g / 1, which simulates an aqueous phase at the outlet of the copper electrolysis circuit, recycled as an aqueous stripping solution, it that is to say used to re-extract the copper contained in the organic phase. The organic phase loaded with copper contains as extracting agent in the three examples of FIG. 3, respectively 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) -pyrazol-3-one (curve 3), LIX 64 N (curve 1) and 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one (curve 2), and in the examples in FIG. 4, respectively 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3 _H ) pyrazol-3-one curve 2) and LIX 64 N (curve 1).

• 1. En ce qui concerne la concentration optimale en agent d'extraction ainsi que le pH de la phase aqueuse le mieux adapté pour qu'on atteigne le maximum d'extraction :
  • - dans le cas d'une solution à faible teneur en cuivre :
    • . à pH 2,5 il n'est pas nécessaire d'utiliser une concentration supérieure à 50 g/1 pour atteindre l'épuisement des phases aqueuses avec un nombre limité d'étages,
    • . par comparaison avec l'agent d'extraction commercial LIX 64 N, les performances de la 2-phényl 4-lauroyl 5-méthyl (3H)-pyrazol-3-one en solution dans le SOLVESSO (concentration 50 g/1) sont équivalentes à celles du LIX 64 N à la concentration de 136 g/1 dans du diluant ESCAID 100 (se reporter au tableau I et aux courbes correspondantes de la figure 2).
  • - dans le cas d'une solution aqueuse sulfurique à forte teneur en cuivre, par'comparaison avec le KELEX 100 à la concentration de 15 % en volume (soit 143 g/1) dans le SOLVESSO 150 additionné de 20 % de nonylphénol, les performances des acylpyrazolones (2-phényl 4-lauroyl [et 4-(2-éthyl hexanoyl)] 5-méthyl (3H) pyrazol-3-one) sont du même ordre de grandeur à concentration équivalente et même encore à une concentration légèrement inférieure (soit 120 à 130 g/1).
  
  (Voir tableau II et figure 3 courbe 1 pour le LIX, 2 pour la lauroylpyrazolone et 3 pour l'hexanoyl.)
• 2. Les isothermes d'extraction tracées de façon à permettre de connaître la capacité de l'agent d'extraction à saturation (voir figure 2) sont pratiquement confondues pour la 2-phényl 4-lauroyl 5-méthyl (3H) pyrazol_-3-one et le LIX 64 N, ce qui confirme l'équivalence des performances entre la "lauroylpyrazolone" à seulement 50 g/l et le _LIX 64 N à la concentration de 15 % en volume, soit 136 g/1.

These tests, the results of which are reported in the abovementioned figures, to which it is useful to refer, show that:

• 1. With regard to the optimal concentration of extraction agent as well as the pH of the aqueous phase best suited for reaching the maximum extraction:
  • - in the case of a solution with a low copper content:
    • . at pH 2.5 it is not necessary to use a concentration greater than 50 g / 1 to achieve the exhaustion of the aqueous phases with a limited number of stages,
    • . by comparison with the commercial extracting agent LIX 64 N, the performances of 2-phenyl 4-lauroyl 5-methyl (3H) -pyrazol-3-one in solution in SOLVESSO (concentration 50 g / 1) are equivalent to those of LIX 64 N at a concentration of 136 g / 1 in ESCAID 100 diluent (see Table I and the corresponding curves in Figure 2).
  • - in the case of an aqueous sulfuric solution with a high copper content, by comparison with the KELEX 100 at a concentration of 15% by volume (i.e. 143 g / 1) in SOLVESSO 150 supplemented with 20% nonylphenol, the performances of acylpyrazolones (2-phenyl 4-lauroyl [and 4- (2-ethyl hexanoyl)] 5-methyl (3H) pyrazol-3-one) are of the same order of magnitude at equivalent concentration and even even at slightly lower concentration (i.e. 120 to 130 g / 1).
  
  (See Table II and Figure 3 curve 1 for LIX, 2 for lauroylpyrazolone and 3 for hexanoyl.)
• 2. The extraction isotherms drawn in such a way as to make it possible to know the capacity of the extraction agent at saturation (see FIG. 2) are practically confused for 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol _- 3 -one and LIX 64 N, which confirms the equivalence of performance between "lauroylpyrazolone" at only 50 g / l and _LIX 64 N at a concentration of 15% by volume, ie 136 g / 1.

The tests carried out made it possible to calculate the following extraction capacities:

We can conclude that, for an equivalent amount, 2 _- phenyl 4-acyl 5-methyl (3H) pyrazol-3-ones have an extraction capacity approximately three times greater than that of LIX 64 N.

3. The isothermal re-extraction curves obtained for comparative re-extraction tests by successive contacts of the same sulfuric aqueous phase with a new organic phase charged with extractable metal species are linear, which proves that the saturation of the aqueous phase does not is not reached (Figures 3 and 4).

The isotherms are similar for 2-phenyl 4-lauroyl 5-methyl pyrazol-3-one and the product of type LIX.

The re-extraction is slightly easier in the case of 2-phenyl 4- (2-ethyl hexanoyl) 5-methyl (3H) pyrazol-3-one. Figure 4 highlights in particular in a case representative of the industrial conditions of use (aqueous phase initially charged with copper) that the copper extraction is more effective in the case of 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3 _H ) pyrazol-3-one than in the case of LIX 64 N.

On the other hand, the selectivity of the extraction, that is to say the separation of Cu and the other metals Fe, Ni, Co, of the assays carried out in the raffinate (spent aqueous phase) and in the organic phase (and the results of which appear from Tables I, II and IV below), have shown that the selectivity is better for the great majority of the products according to the invention than by using commercial products as extractants, i.e. LIX 64 N or the one called KELEX 200.

• où [M] org représente la concentration du métal M dans la phase organique
• et [M] aq la concentration du métal M dans la phase aqueuse.

In particular, the Cu / Fe selectivity was calculated in Table IV after 10 minutes of extraction. This selectivity is equal to the ratios of the extraction constants

• where [M] org represents the concentration of metal M in the organic phase
• and [M] aq the concentration of metal M in the aqueous phase.

Since the iron and copper concentrations are initially the same, another way of expressing selectivity is to carry out the ratio [Cu] org: [Fe] org.

This selectivity is confirmed by the results of the determination of iron and copper in aqueous solutions resulting from the sulfuric re-extraction (H ₂ S0 ₄ 1N) (Table III below) and the determination of these same elements in the corresponding organic phase.

Indeed, in the presence of acylpyrazolone, practically 10 times less iron is extracted than in the presence of LIX 64 N, while the quantities of copper extracted are practically the same.

The selectivity towards nickel and cobalt is even better. Indeed, these metals are not extracted with 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one in solution in SOLVESSO 150 (concentration 40 g / 1), from a solution aqueous sulfuric where they are present at a concentration of about 3 g / 1.

This selectivity is further confirmed by the results of the treatment of a sulfuric solution with a high copper content (23 g / 1), additionally containing 6 g / 1 of Fe, 18 g / 1 of Ni and 1 g / 1 of Co , with 2-phenyl 4- (2-ethyl hexanoyl) 5-methyl (3H) pyrazol-3-one in diluent SOLVESSO 150 and at the concentration of 0.42 mol per liter.

The charged organic phase contained (see example 10 below):

Example 11 below relates to a comparison between 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one and the commercial product called KELEX 100, and further demonstrates the best selectivity obtained in l extraction of Cu in the presence of iron, nickel and cobalt with the pyrazolone according to the invention.

The invention is illustrated in more detail in the examples below, which do not limit it in any way.

Example 1

Extraction of copper from low content solutions, pH 2.5, with 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one.

An aqueous sulfuric solution, at pH 2.5, containing 2.9 g / 1 of copper (Cu ²⁺ ) and 3.2 g / 1 of iron is brought into contact with a solution of 2-phenyl 4-lauroyl 5- methyl (3H) pyrazol-3-one at 100 g / 1 in SOLVESSO 150, without additive of the nonyphenol type.

The extraction is carried out, volume by volume, in a separating funnel, at 20 ° C., with mechanical stirring for half an hour. The pH of the equilibrium aqueous solution is then measured.

After decantation, the copper and iron contents of the residual aqueous phase (called raffinate) are measured by atomic absorption. The metal contents of the organic phase are calculated by difference.

The results obtained are as follows:

Example 2

Extraction of copper from low content solutions, pH = 1, with 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one.

A sulfuric aqueous solution, pH 1, containing 2.9 g / 1 copper _Cu ²⁺ and _{3, 2} g _{/ 1 iron} is contacted, volume for volume, with a solution of 2-phenyl-4-lauroyl-5 -methyl (3H) pyrazol-3-one at 100 g / 1 in SOLVESSO 150, without addition of nonylphenol.

The extraction and the assays are carried out as in Example No. 1.

The results are as follows:

Example 3

Extraction of copper from a low content solution, pH 2.5, with 2-phenyl 4- (2-ethyl hexanoyl) 5-methyl (3H) pyrazol-3-one.

An aqueous sulfuric solution, pH 2.5, containing 3 g / 1 of copper Cu ²⁺ and 3.2 g / 1 of iron is brought into contact, volume by volume, with a solution of 2-phenyl 4- (2 -ethyl hexanoyl) 5-methyl (3H) pyrazol-3- one at 42 g / 1 in SOLVESSO 150.

The extraction and the assays are carried out as in Example No. 1.

The results are as follows:

Example 4

Extraction of copper from a low content solution, pH = 2.5, with 2-phenyl 4-stearoyl 5-methyl (3H) -pyrazol-3-one.

An aqueous sulfuric solution at pH 2.5, containing 2.9 g / 1 of copper Cu ²⁺ and 3.2 g / 1 of iron is brought into contact, volume by volume, with a solution of 2-phenyl 4-stearoyl 5-methyl (3H) pyrazol-3-one at 62 g / 1 in SOLVESSO 150 with 10 ml / 100 ml of nonylphenol.

The extraction and the assays are carried out as in Example No. 1.

The results are as follows:

Example 5

Extraction of copper from a low content solution, pH 2.3, with 2,5-diphenyl 4- (oleoyl) (3H) pyrazol-3-one.

An aqueous sulfuric solution, at pH 2.3, containing 3.2 g / 1 of copper Cu ²⁺ and 3.35 g / 1 of iron is brought into contact, volume by volume, with a solution of 2.5 diphenyl 4 - (oleoyl) (3H) pyrazol-3-one at 50 g / 1 in SOLVESSO 150.

The extraction is carried out as in example n ° 1. The assays are carried out by measuring the copper and iron contents, by atomic absorption, in the aqueous and organic phases.

Example 6

Extraction of copper from a low pH 2.3 solution with 2-phenyl 4- (undecenoyl) 5-methyl (3H) pyrazol-3-one.

An aqueous sulfuric solution, at pH 2.3, containing 3.13 g / l of copper Cu ²⁺ and 3.21 g / 1 of iron is brought into contact, volume by volume, with a solution of 2-phenyl 4- (undecenoyl) 5-methyl (3 _H ) pyrazol-3- one at 50 g / 1 in SOLVESSO 150, with 10% by volume of nonylphenol.

The extraction and the assays are carried out as in Example No. 5.

Example 7

Extraction of copper from a low content solution, pH 2.3, with 2-phenyl 4-lauroyl 5-n propyl (3H) pyrazol-3-one

An aqueous sulfuric solution, at pH 2.3, containing 3.13 g / 1 of copper Cu ²⁺ and 3.21 g / 1 of iron is brought into contact, volume by volume, with a solution of 2-phenyl 4- lauroyl 5-n propyl (3H) pyrazol-3-one at 50 g / 1 in SOLVESSO 150, with 10% by volume of nonylphenol.

The extraction and the assays are carried out as in Example No. 5.

Example 8

Extraction of copper from a low content solution, pH 2.5, with 2,5 diphenyl 4- (lauroyl) (3H) pyrazol _- 3-one

An aqueous sulfuric solution, at pH 2.5, containing 3 g / 1 of copper Cu ²⁺ and 3 g / 1 of iron is brought into contact, for 1/2 hour, volume to volume, with a 0.14 M solution. (50.6 g / 1) of 2.5 diphenyl 4- (lauroyl) (3H) pyrazol-3-one in SOLVESSO 150, with 10% nonylphenol volume by volume.

The extraction and the assays are carried out as in Example No. 5.

Example 9

Extraction of copper from a medium content solution, pH 2.3, with 2-phenyl 4 (2-ethylhexanoyl) 5-methyl (3H) pyrazol-3-one.

An aqueous sulfuric solution, at pH 2.3, containing 6.16 g / 1 of copper Cu ²⁺ and 1.24 g / 1 of iron is brought into contact, for 1/2 hour, volume to volume, with a solution 100 g / l of 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) pyrazol-3-one in SOLVESSO 150 with 2% nonylphenol (volume to volume).

The extraction and the assays are carried out as in Example No. 5.

Example 10

Extraction of copper from a high content solution, pH = 2, by 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) pyrazol-3-one.

An aqueous sulfuric solution, at pH 2, containing 23 g / 1 of copper, 6 g / 1 of iron, 18 g / 1 of nickel and 1 g / 1 of cobalt is brought into contact with a solution of 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) pyrazol-3-one at 126 g / 1 in SOLVESSO 150.

The extraction is carried out in a separating funnel, with mechanical stirring for half an hour. The elements are dosed by atomic absorption either in the residual aqueous phase (raffinate), or, to increase the sensitivity of the measurement, for some in an aqueous re-extraction phase (H ₂ SO ₄ lN).

The results are as follows:

Example 11

Extraction of copper from a high content solution, pH 2, with 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one.

An aqueous sulfuric solution, at pH 2, containing 22.6 g / 1 of copper, 6.1 g / 1 of iron, 19.2 g / 1 of nickel and 0.8 g / 1 of cobalt is brought into contact, volume by volume, at 20 ° C, with a solution of 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one at 150 g / 1 in SOLVESSO 150.

The extraction is carried out in a separating funnel, with stirring for half an hour. The elements are dosed by atomic absorption in the residual aqueous phase (raffinate) and the extraction rates are evaluated by difference.

A titre de comparaison, l'extraction de la même solution acide par le KELEX 100 à 143 g/1 dans le SOLVESSO 150 (avec 20 ml/100 ml de nonylphénol) donne les résultats suivants :

The results are as follows:

By way of comparison, the extraction of the same acid solution with KELEX 100 at 143 g / 1 in SOLVESSO 150 (with 20 ml / 100 ml of nonylphenol) gives the following results:

Example 12

Extraction capacity of 2-phenyl 4-acyl 5-methyl (3H) pyrazol-3-ones.

The extraction isotherms are produced by successive contacts of the same organic phase with a new aqueous phase under the following conditions:,

Aqueous phase: sulfuric solution at pH 2.5 of 3 g / 1 of copper and 3 g / 1 of iron.

Initial organic phase 50 g / l solution of acyl pyrazolone in SOLVESSO 150 with 10 ml / 100 ml of nonylphenol (except for 2- phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) pyrazol-3 -one where no nonylphenol is added).

The extractions are carried out volume by volume, at 20 ° C. in separating funnels, with, each time, a contact for half an hour with stirring. The copper is measured by atomic absorption in the residual aqueous phases (raffinate) and the copper concentration in the organic phases is evaluated by difference.

• pour la 2-Phényl 4-lauroyl 5-méthyl (3H)pyrazol-3-one : 80 mgCu/g extractant ;
• 2-phényl 4-stéaroyl 5-méthyl (3H)pyrazol-3-one : 70 mgCu/g
• 2-phényl 4-(2-éthyl hexanoyl) 5-méthyl (3H)-pyrazol-3-one : 90 mgCu/g
• 2-phényl 4-isononanoyl 5-méthyl (3H)pyrazol-3-one : 104 mgCu/g

From the extraction isotherms, the capacity of the extractant at saturation is calculated by dividing the maximum load (in g of metal per liter) assessed on the isotherm by the concentration of the supposed pure extractant expressed in g / 1 .

• for 2-Phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one: 80 mgCu / g extractant;
• 2-phenyl 4-stearoyl 5-methyl (3H) pyrazol-3-one: 70 mgCu / g
• 2-phenyl 4- (2-ethyl hexanoyl) 5-methyl (3H) -pyrazol-3-one: 90 mgCu / g
• 2-phenyl 4-isononanoyl 5-methyl (3H) pyrazol-3-one: 104 mgCu / g

For comparison, the extraction capacity of LIX 64 N, at 136 g / liter in ESCAID 100 is 30 mgCu / g of extractant.

Example 13

Extraction in the case of 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one.

• les isothermes de réextraction sont réalisées par contacts successifs d'une même phase aqueuse H₂S0₄ (lN) avec une nouvelle phase organique contenant 50 g/1 de 2-phényl 4-lauroyl 5-méthyl(3H)pyrazol-3-one dans du SOLVESSO 150 contenant 10 ml/100 ml de nonylphénol et 4 g/1 de cuivre ; l'équilibre correspondant aux plus faibles concentrations est obtenu par épuisement de la phase organique résultant du premier contact par une phase aqueuse vierge.

The re-extraction was carried out under the following conditions:

• the re-extraction isotherms are carried out by successive contacts of the same aqueous phase H ₂ S0 ₄ (lN) with a new organic phase containing 50 g / 1 of 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one in SOLVESSO 150 containing 10 ml / 100 ml of nonylphenol and 4 g / 1 of copper; the equilibrium corresponding to the lowest concentrations is obtained by exhaustion of the organic phase resulting from the first contact with a virgin aqueous phase.

The contacts take place in separating funnels, at 20 ° C for half an hour. The concentrations are determined by atomic absorption, both in the aqueous phases and in the organic phases (after dilution in ethanol for the latter). The extraction isotherms are gathered in FIG. 3, where curve 1 relates to LIX 64N at 136 g / 1 in ESCAID 100 and curve 2 relates to 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3- one.

Example 14

Extraction in the case of 2-phenyl 4- (2-ethyl hexanoyl) 5-methyl (3H) pyrazol-3-one.

The procedure was as indicated in Example 13. The re-extraction isotherm was established from the results obtained following successive contacts (volume to volume) of the same aqueous phase H ₂ SO ₄ (1N) with a new organic phase containing the extractant at a concentration of 0.14 mole / 1, or 42 g / 1, and copper at a rate of 3.3 g / 1 in SOLVESSO 150 and without nonylphenol.

The contacts took place in separating funnels, with stirring, for half an hour, at room temperature.

The assays of copper and iron were carried out by atomic absorption in the aqueous re-extraction phases.

The isotherm drawn is linear and gives values slightly higher than those with LIX 64N and 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one (Figure 3, curve 3).

Example 15

Extraction with an aqueous stripping solution containing 30 g / l of copper. 2-phenyl 4- (ethyl 2-hexanoyl) 5-methyl (3H) pyrazol-3-one.

The re-extraction was carried out under the following conditions: the re-extraction isotherms are determined by successive contacts of the same aqueous phase (H ₂ S0 ₄ 3N, Cu 30 g / 1) with a new organic phase containing 50 g / 1 of 2 -phenyl 4- (ethyl 2-hexanoyl) 5-methyl (3H) pyrazol-3-one in SOLVESSO 150 containing 10 ml / 100 ml of nonylphenol and 3.5 g / 1 of copper.

The contacts take place in a separating funnel, at 20 ° C, for half an hour. The concentrations are determined by atomic absorption, both in the aqueous phases and in the organic phases (after dilution in ethanol for the latter). The extraction isotherms are gathered in FIG. 4 where layer 1 relates to LIX 64N (at 15% in ESCAID 100) and curve 2 to 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) pyrazol-3-one.

Example 16 Copper / iron selectivity

The copper-iron selectivity was studied by assaying iron in the H ₂ S0 ₄ lN re-extraction solutions obtained as described in Example 13, the initial aqueous solution with low copper content, at pH 2.5, containing 3 g / 1 of copper and 3 g / 1 of iron.

• 2-phényl 4-lauroyl 5-méthyl (3H) pyrazol-3-one Cu : 11,9 g/1 Fe : 0,032 g/1
• 2-phényl 4-(2-éthyl hexanoyl) 5-méthyl (3H) pyrazol-3-one Cu : 11,5 g/1 Fe : <0,01 g/1
• LIX 64 N Cu : 13,8 g/1 Fe : 0,310 g/1

For the final solutions with the highest copper content, the following results are obtained:

• 2-phenyl 4-lauroyl 5-methyl (3H) pyrazol-3-one Cu: 11.9 g / 1 Fe: 0.032 g / 1
• 2-phenyl 4- (2-ethyl hexanoyl) 5-methyl (3H) pyrazol-3-one Cu: 11.5 g / 1 Fe: <0.01 g / 1
• LIX 64 N Cu: 13.8 g / 1 Fe: 0.310 g / 1

Example 17

Extraction of copper and iron by 4-acyl (3H) pyrazol-3-ones Comparative selectivity

• La solution aqueuse de sulfate de cuivre à 3 g/1 de cuivre (Cu²⁺) et de sulfate de fer à 3 g/1 de fer est ajustée à pH 2,5 par ajout de ^H ₂S0₄ sous contrôle potentiométrique.

All 4-acyl (3H) pyrazol-3-ones are studied according to the same operating process:

• The aqueous solution of copper sulphate at 3 g / 1 of copper (Cu ²⁺ ) and of iron sulphate at 3 g / 1 of iron is adjusted to pH 2.5 by adding ^H ₂ S0 ₄ under potentiometric control.

50 ml of this solution are poured into a cell thermostatically controlled at 25 ° C provided with magnetic stirring. To this solution is slowly poured 50 ml of the organic extraction phase (0.14 mole of 4-acyl (3H) pyrazol-3-one into SOLVESSO 150 with or without, depending on the case, 10% of nonylphenol (V / V)) avoiding any agitation.

Finally the magnetic stirring, previously set at 750 rpm, is put into operation.

Intermediate samples, in the aqueous and organic phases, at times 3.10 and 60 minutes are taken to measure, by atomic absorption, the quantities of iron and copper extracted.

The results are collated in Table IV, expressed as a percentage of extraction relative to the quantity initially present in the aqueous solution.

Example 18

Preparation of 2-phenyl 4- (2-ethyl hexanoyl) 5-methyl (3H) pyrazol-3-one.

A mixture of 1044 g (6 moles) of 2-phenyl 5-methyl (3H) pyrazol-3-one in 4 l of dioxane is stirred and the temperature is brought to 60 ° C to achieve complete dissolution of the pyrazolone. Then added 888 g (12 moles) of calcium hydroxide Ca (OH) ₂ and then in 45 minutes, 876 g (5.4 moles) of 2-ethyl hexanoyl chloride. The medium heats up to 95 ° C, this temperature is maintained and stirring for 2 hours.

After cooling, the reaction mixture is poured into 8 l of HCl (2N). An organic layer separates, 2 l of toluene are added to facilitate decantation;

The organic phase is dried over magnesium sulfate and the solvent removed under reduced pressure.

• - Le rendement en produit purifié est de 61%.
• - L'identification a été réalisée 1 - par RMN(H).

The oily residue obtained with a yield of 77% is rectified on a vacuum distillation apparatus with a thin film. The product distills at 162 ° C under 0.1 Pa.

• - The yield of purified product is 61%.
• - The identification was carried out 1 - by NMR (H).

• - à 2,5 ppm : singulet correspondant au CH₃ en position 5 sur le noyau pyrazol,
• - entre 0,7 et 3,1 ppm : multiplets attribués au reste alkyl,
• - entre 7,2 et 8 ppm : multiplets du noyau aromatique,
• - à 14 ppm : singulet correspondant au proton énolique.

The NMR spectrum, produced in CDC1 ₃ solvent, with the TMS as reference having the following peaks:

• - at 2.5 ppm: singlet corresponding to CH ₃ in position 5 on the pyrazol ring,
• - between 0.7 and 3.1 ppm: multiplets attributed to the alkyl residue,
• - between 7.2 and 8 ppm: multiplets of the aromatic nucleus,
• - at 14 ppm: singlet corresponding to the enolic proton.

2 - by elementary analysis

3 - refractive index n2 ⁰ = 1.5560

4 - density at 20 ° C: 1.0678

Example 19 Preparation of 2-phenyl 4-isononanoyl 5-methyl (3H) pyrazol-3- one

• 0,9 à 1,4 ppm(m) ; 2,5 ppm(s) ; 2,6 à 2,8 ppm(m) ;
• 7,2 à 8,1 ppm(m) ; 13,5 ppm(s).

By following the procedure of Example 18, with the same proportions but by replacing 2-ethyl hexanoyl chloride with isononanoyl chloride, 2-phenyl 4-isononanoyl 5-methyl (3H) pyrazol-3 is obtained. -one with a yield of 75%. This compound distills at 165 ° C at 0.1 Pa. The NMR spectrum plotted in CDCl ₃ , with the TMS reference, presents the peaks:

• 0.9 to 1.4 ppm (m); 2.5 ppm (s); 2.6 to 2.8 ppm (m);
• 7.2 to 8.1 ppm (m); 13.5 ppm (s).

Example 20

Preparation of di 1,6 (2-phenyl-5-methyl 4-pyrazolyl-3-one) hexane-1,6-dione.

0.225 mole (39.15 g) of 2-phenyl 5-methyl pyrazol-3-one is dissolved in 250 cm ³ of dioxane. 0.4 mol of Ca (OH) ₂ (29.6 g) is added and then 0.1 mol of adipoyl chloride ClCO (CH ₂ ) ₄ COC1 (18.3 g) is rapidly added. It is brought to reflux for 3/4 hour.

The reaction mixture is poured into 1.2 liters of 2N hydrochloric acid. The solid product which precipitates is separated and redissolved in methylene chloride. The organic solution is dried over magnesium sulfate and then evaporated. A solid product is obtained with a melting point of 203 ° C., the mass spectrum of which has a molar peak (M + 1) at 459.

Example 21

Preparation of 2-phenyl 4- (oleoyl) 5-phenyl (3H) pyrazol-3-one.

0.2 mol, or 47.2 g, of 2-phenyl 5-phenyl pyrazol-3-one is dissolved in 600 cm ³ of dioxane at a temperature of 60 ° C. 0.4 mole of lime (29.6 g) is added and then over 30 minutes 0.2 mole of oleoyl chloride. The temperature of the reaction mixture is raised to 95 ° C and allowed to stir for 2 hours.

The cooled mixture is poured into 1 liter of hydrochloric acid (2N). An oil separates; it is taken up in methylene chloride. This organic phase is dried, then the solvent is removed under vacuum.

An oily product is recovered with a yield of 84.5%. Purification was carried out by isolating the cobalt complex from oleo-ylpyrazolone.

50 g of crude derivative, ie 0.1 mole, are mixed in 100 cm ³ of methanol with 0.055 mole of anhydrous cobalt acetate, ie 9.73 g. The mixture is brought to reflux for 30 minutes.

The cobalt salt of oleoyl pyrazolone precipitates in methanol, it is filtered and washed with water.

This salt is placed in methylene chloride and, with stirring, sulfuric acid (3N) is introduced so as to destroy the cobalt complex and release the oleoyl pyrazolone which is then dissolved in methylene chloride.

This organic phase is separated, washed with water, dried, and the solvent removed under reduced pressure.

The oil obtained corresponds to pure oleoyl pyrazolone, the identification of which was carried out by NMR (triplet of ethylenic protons between 5.2 and 5.5 ppm).

Example 22

Preparation of 2-phenyl 4- (undecenoyl) 5-methyl (3H) pyrazol-3-one.

Following the procedure of Example 18, with the same proportions, but replacing the 2-ethyl hexanoyl chlorule with undecenoyl chloride, a solid derivative is obtained which, after recrystallization from hexane, has a melting point. 40 ° C.

• - 1 singulet à 2,5 ppm correspondant au méthyl en position 5 sur le cycle pyrazol ;
• - 1 triplet entre 2,6 et 2,9 ppm correspondant aux protons méthyléniques en α du groupement carbonyle ;
• - 1 doublet entre 1,9 et 2,1 ppm attribué aux protons méthyléniques en α de l'insaturation
• - entre 0,9 et 2,4 multiplets correspondant aux protons restants de la chaîne alkyl ;
• - entre 4,8 et 6,1 ppm multiplets attribués aux protons portés par la double liaison ;
• - entre 7,1 et 8 ppm multiplets des protons aromatiques ;
• - 14,5 ppm singulet provenant du proton énolique.

On the NMR spectrum, with TMS as reference and in CDCl ₃ solvent, the following peaks are identified:

• - 1 singlet at 2.5 ppm corresponding to methyl in position 5 on the pyrazol ring;
• - 1 triplet between 2.6 and 2.9 ppm corresponding to the methylenic protons at α of the carbonyl group;
• - 1 doublet between 1.9 and 2.1 ppm attributed to the methylenic protons in α of the unsaturation
• - between 0.9 and 2.4 multiplets corresponding to the remaining protons of the alkyl chain;
• - between 4.8 and 6.1 ppm multiplets attributed to the protons carried by the double bond;
• - between 7.1 and 8 ppm multiplets of aromatic protons;
• - 14.5 ppm singlet from the enolic proton.

Example 23

Preparation of di 1.10 (2-phenyl-5-phenyl 4-pyrazolyl-3-one) decane-1.10 dione.

0.2 mol or 47.2 g of 2-phenyl 5-phenyl pyrazol-3-one is dissolved in 600 cm ³ of dioxane, at a temperature of 60 ° C. 0.4 mole of lime Ca (OH) ₂ (29.6 g) is added, then 0.09 mole of sebacoyl chloride, or 21.5 g, over 30 minutes. The temperature of the medium is 95 ° C .; it is maintained for 2 hours.

After cooling, the reaction mixture is poured into 1 liter of hydrochloric acid (2N).

The solid which precipitates is redissolved in 200 cm ³ of methylene chloride.

The organic solution is washed twice with 200 cm ³ of H ₂ S0 ₄ (3N) and then with distilled water. It is then dried and the solvent removed under reduced pressure.

The solid product obtained, with a yield of 49.3% has a melting point of 168 ° C and exhibits in NMR a spectrum in agreement with the formula of the compound.

Example 24 Preparation of 2-phenyl 4- (lauroyl)) 5-phenyl (3H) pyrazol-3-one

• - L'identification à été effectué par RMN.
• - La pureté a été controlée par anolyse élémentaire.
  

Following the procedure of Example 18, with the same proportions but replacing 2-phenyl-5-methyl (3H) pyrazol-3-one, with 2-phenyl 5-phenyl (3H) pyrazol-3- one (Mw = 136.3 g; mp = 136 ° _C ) and 2-ethyl hexanoyl chloride with lauroyl chloride, a solid product is obtained which after recrystallization from hexane has a melting point of 69 ° C .

• - The identification was carried out by NMR.
• - The purity was checked by elementary anolysis.
  

Example 25 Preparation of 2-phenyl 4- (lauroyl) 5-propyl (3H) pyrazol-3-one

According to the procedure of Example 18, with the same proportions, but replacing 2-phenyl 5-methyl (3H) pyrazol-3-one with 2-phenyl 5-propyl (3H) pyrazol-3-one ( Mw = ₂₀₂ ; mp = 114 °) and 2-ethyl hexanoyl chloride with lauroyl chloride, a solid product is obtained which, after recrystallization from hexane, has a melting point of: 61 ° C.

• - 0,7 à 2,8 ppm (multiplets des CH₃ et CH₂)
• - 7,2 à 8,1 ppm (multiplets des H aromatiques)
• - 14,5 ppm (singulet du proton énolique)

The NMR spectrum plotted in CDCl ₃ with TMS as reference presents the characteristic peaks of 2-phenyl 4- (lauroyl) 5-propyl (3H) pyrazol-3-one:

• - 0.7 to 2.8 ppm (multiplets of CH ₃ and CH ₂ )
• - 7.2 to 8.1 ppm (multiplets of aromatic H)
• - 14.5 ppm (singlet of the enolic proton)

Example 26 Affinity of 4-acyl (3H) pyrazol-3-ones for the cation Fe ³⁺

• Une solution aqueuse de sulfate ferrique Fe₂(SO₄)₃ à 7,5 g/1 de Fe³⁺ est ajustée à pH2 par ajout éventuel de H₂S0₄ sous contrôle potentiométrique.

All 4-acyl (3H) pyrazol-3-ones are studied according to the same operating process:

• An aqueous solution of ferric sulfate Fe ₂ (SO ₄ ) ₃ at 7.5 g / 1 of Fe ³⁺ is adjusted to pH2 by optional addition of H ₂ S0 ₄ under potentiometric control.

This aqueous phase is brought into contact, for 15 minutes, with stirring in a separating funnel, with a solution of 4-acyl (3H) pyrazol-3-one (0.2 M in SOLVESSO 150, without nonylphenol additive). The extraction is carried out, volume to volume, at room temperature.

The assays are carried out by measuring the iron contents, by atomic absorption, in the aqueous and organic phases.

The results are collated in Table V. There is a significant affinity of 4-acyl (3H) pyrazol-3-ones with iron when R ₁ is an aliphatic chain or when ZR ₃ is aromatic. The corresponding 4-acyl pyrazolones therefore do not allow a selective extraction of copper from iron.

Example 27

Extraction of copper and iron with 2-phenyl 4-thénoyl 5-methyl (3H) pyrazol-3-one

The extraction is carried out as in Example No. 17: a 0.14 M solution of 2-phenyl 4-thénoyl 5-methyl (3H) pyrazol-3-one in SOLVESSO 150 without nonylphenol is brought into contact with a aqueous sulfuric solution with 3 g / 1 of copper Cu ²⁺ and 3 g / 1 of iron (pH 2.5).

• - Cu extrait : 71 %
• - Fe extrait : 7,9%
• - [Cu] org : [F]_org ≃ 9, soit une mauvaise sélectivité vis-à-vis du fer.

After dosing the copper and iron elements in the 2 phases, the results are as follows after 3 minutes of extraction:

• - Cu extracted: 71%
• - Fe extracted: 7.9%
• - [Cu] org: [F] _org ≃ 9, that is, a poor selectivity with respect to iron.

Example 28

Extraction of copper and iron with 2-n lauryl 4-lauroyl 5-methyl (3H) pyrazol-3-one

The extraction is carried out as in Example No. 17: a 0.14 M solution of 2-n lauryl 4-lauroyl 5-methyl (3H) pyrazol-3-one in SOLVESSO 150, without nonylphenol as an additive, is brought into contact with an aqueous sulfuric phase containing 3 g / 1 of copper Cu ²⁺ and 3 g / 1 of iron (pH 2.5).

• - Cu extrait : 48,8 %
• - Fe extrait : 6,9 %
• - [Cu]_org : [Fe]_org ≃ 7, soit une mauvaise sélectivité vis-à-vis du fer.

After determination of the copper and iron elements, by atomic absorption, in the 2 phases, the results are as follows, after 60 minutes of extraction:

• - Cu extracted: 48.8%
• - Fe extracted: 6.9%
• - [Cu] _org : [Fe] _org ≃ 7, or a poor selectivity with respect to iron.

Example 29

Copper and iron extraction with 2-phenyl 4-benzoyl 5-methyl (3H) pyrazol-3-one

An organic phase containing 2-phenyl 4-benzoyl 5-methyl (3H) pyrazol-3-one 0.14 M in SOLVESSO 150, with 10% nonylphenol, is stirred, volume to volume, in a vial. decant, with an aqueous sulfuric phase at pH 2.5 containing 3 g / 1 of copper Cu2 + and 3 g / 1 of iron. Agitation lasts half an hour at room temperature.

• - Cu extrait : 97%
• - Fe extrait : 40%
• - [Cu]_org : [Fe]_org ≃ 2,5, soit pratiquement aucune sélectivité vis-à-vis du fer.
  
  
  
  
  

A precipitate of the complex with copper immediately appears. The assays are carried out, on the aqueous phases, by atomic absorption. The results are as follows:

• - Cu extracted: 97%
• - Fe extracted: 40%
• - [Cu] _org : [Fe] _org ≃ 2.5, ie practically no selectivity with respect to iron.
  
  
  
  
  

Claims (7)

1. A method for the selective extraction of copper of the liquid / liquid type from an aqueous sulfuric solution for attacking the ore or a concentrated semi-product, characterized in that at least one extraction agent is used. type 4-acyl (3H) pyrazol-3-one in solution in an organic solvent, preferably dissolving the complex formed between the extracting agent and the copper. 2. Method according to claim 1, characterized in that the extracting agent corresponds to formula (A) or to the corresponding keto-enolic forms.

- where R ₁ represents a phenyl group, optionally substituted by one or more alkyl groups each containing 1 to 12 carbon atoms; - where R ₂ represents a branched or unbranched alkyl group containing 1 to 12 carbon atoms, a phenyl group optionally substituted by one or more alkyl groups each containing 1 to 12 carbon atoms; - where Z represents a linear or branched, saturated or unsaturated alkylene group containing from 1 to 21 carbon atoms; - And where R ₃ represents H, a (2-phenyl 5-alkyl (3H) pyrazolyl _- 3-one) carbonyl-4 or a (2-phenyl 5-phenyl (3H) pyrazolyl-3-one) carbonyl-4 for form a bis (acyl pyrazolone), the phenyls possibly being substituted or not by alkyl groups. 3. Method according to claim 1, characterized in that an organic solvent practically insoluble in water is used, not disturbing the complexing action of the extractant and having a high flash point. 4. Method according to claim 3, characterized in that the organic solvent is chosen from aliphatic or aromatic hydrocarbons with a high flash point, in particular kerosene, naphtha and the like. 5. Method according to any one of the preceding claims, characterized in that the extraction agent is at a concentration between 20 g / 1 and 750 g / 1 in the solvent and preferably between 50 g / 1 and between 200 g / 1. 6. Method according to any one of the preceding claims, characterized in that the extraction solution additionally contains from 2 to approximately 20 ml / 100 ml of nonylphenol, and preferably approximately 10 ml / 100 ml. 7. 2-Phenyl 4-acyl pyrazol-3-one derivatives, corresponding to the general formula (A), characterized in that they are chosen from the following compounds: - 2-phenyl 4- (2-ethylhexanoyl) 5-methyl (3H) pyrazol-3-one - 2-phenyl 4- (isononanoyl) 5-methyl (3H) pyrazol-3-one - di 1,6- (2-phenyl 5-methyl 4-pyrazolyl-3-one) hexal 1,6-dione - 2-phenyl 4 (undecenoyl) 5-methyl (3H) pyrazol-3-one - 2-phenyl 4- (oleoyl) 5-phenyl (3H) pyrazol-3-one - di-1,10- (2-phenyl 5-phenyl 4-pyrazolyl-3-one) decane 1.10 dione.

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